Condensation product and method



Patented Jan. 30, 1940 UNITED STATES PATENT OFFICE No Drawing. Application December 22, 1936,

' Serial No. 117,243

22 Claims.

My invention relates to methods of producing an improved condensation product suitable for use in resins, lacquers, paints, varnishes, enamels, metallic coatings, plastic masses, dispersing,

l wetting and softening agents, and for other similar purposes, and to the new product so produced. My invention also relates to the new methods of coating, dispersing, and the like. This application is a continuation in part of my I. copending application, Serial No. 759,086, filed December 24, 1934, for Condensation product and method. Subject matter originally included in this application has been embodied in continuations in part, Serial No. 165,898, filed September I. 27, 1937, for Condensation product and method;

Serial No. 165,899, filed September 27, 1937, for

Condensation product and method; and. Serial No. 165,900, filed September 27, 1937, for Coating composition and method.

Subject matter at one time included in the present application is now included in several copending applications. Serial No. 165,898, filed Sept. 27, 1937, for Condensation product and method, relates to salts and esters of the conden- 25 sation product generally and water soluble salts specifically. Serial No. 165,899, filed Sept. 27, 1937, for Condensation product and method, includes the subject matter relating to reoondensation. Serial No. 165,900, filed Sept. 27, 1937,

for Coating composition and method, is concerned particularly with coating. Serial No. 231,759, filed Sept. 26, 1938, for Condensation product and method, is directed to the reaction product of the condensation product with a basic dyestufi. Serial No. 231,760, filed Sept. 26, 1938, for Condensation product and method, is directed to water insoluble metallic salts. Serial No. 231,761, filed Sept. 26, 1938, for Oily dispersion material, covers oils, fats and waxes emulsified by the condensation product of the invention. Serial No. 235,252, filed October 15, 1938, for Condensation product and method, is directed to condensation with oleic acid and its compounds.

A purpose of my invention is to produce an improved condensation product by causing condensation between one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, and one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in the carbon chains;

- .nonhydroxylated salts thereof; nonhydroxylated 5 esters thereof or similar compounds.

A further purpose is to cause maleic anhydride or the like to attach to the carbon chain. of a nonconjugated unsaturated nonhydroxylated fatty acid or the like by suitable application of heat and, desirably also, pressure. A temperature of between C. and 300 C. is preferred for the reaction, 180? C. to 260 C. being the most satisfactory range. For many purposes the reaction will be performed at a temperaturenot less 15 than 150 C. and in excess of the ordinary boiling point of the one of the first group with return condensation.

A further purpose is to cause the acid group of a condensation product of maleic anhydride or the like with a nonconjugated unsaturated nonhydroxylated fatty acid or the like having from ten to twenty-four carbon atoms in its carbon chain to react with other compounds, such as metal salts or metals.

A further purpose is to produce oil soluble driers bycausing a metal or metal salt to combine with the acid portion of a condensation product produced from maleic anhydride or the like and a nonconjugated unsaturated nonhydroxylated fatty acid or the like having from ten to twentyfour carbon atoms in its carbon chain.

Y A further purpose is to produce an air-drying or thermo-hardening metal coating which gives improved adherence to metals and other substances by combining maleic anhydride or the like with a nonconjugated unsaturated nonhydroxylated drying oil or the like, so that the effect of the acid in combining with the substance coated is available to produce good adherence.

A further purpose is to improve the mixing of oil with pigment, facilitate grinding of the pigment, secure controlled penetration of the vehicle, and obtain better leveling properties in a paint by employing a condensation product of-maleic anhydride or the like and a nonconjugated unsaturated nonhydroxylated fatty oil as a vehicle or as an addition to other vehicles.

, A further purpose is to body the condensa- "tion product of maleic anhydride or the like with so a drying oil such as linseed oil, for paint and varnish purposes, by blowing and/or heating the condensation product in the presence or absence of a drier.

Further purposes appear in the specification and in the claims.

It has been known for some time that maleic anhydride or substances yielding maleic anhydride will condense with carbon chain compounds containing a conjugated system of double bonds. For example, Morrell, Marks and Samuels in British Patent No. 407,957 disclose a condensation of maleic anhydride with tung oil, a conjugated compound.

I have discovered that, under suitable conditions, maleic anhydride will react with nonconjugated unsaturated nonhydroxylated fatty oils and acids and similar compounds having from ten to twenty-four carbon atoms in the carbon chain to produce a wide variety of products depending upon the characters of the reacting substances and the subsequent reactions to which the condensation products are subjected.

To produce the maleic condensation product, the maleic grouping must be present in condensable form, preferably as maleic anhydride. The condensation is of course obtained from any of the compounds which yield maleic anhydride and the like, such as malic acid, fumaric acid, maleic acid, aconitic acid or citric acid, if subjected to the conditions under whih maleic anhydride is produced. The production of maleic anhydride from such other acids is well known in the art (Bernthsen, Textbook of Organic Chemistry (1923) pages 250-256). Instead of maleic anhydride, an ester of maleic acid, whether an acid or completed ester, or an alkyl substituted maleic acid having less than ten carbon atoms in its 1 carbon chain such as citraconic anhydride may be used. Maleic acid, maleic anhydride, citraconic anhydride, and various other alkyl substituted maleic acids having less than ten carbon atoms in the carbon chain are all acylic monoolefinic dicarboxylic acids having less than ten carbonic atoms in their carbon chains.

Wherever reference is made herein to maleic anhydride, it will be understood that I include substances which yield maleic anhydride if subjected to the conditions at which maleic anhydride is produced. I also include substituted maleic acids having less than ten carbon atoms in their carbon chains, and other equivalents.

Wherever I refer'herein to an acid or to an acid group, I of course include an acid anhydride and an acid anhydride group, and vice versa. Wherever I refer to an ester, I include also a half ester.

Investigation of a large number of compounds has shown that condensation with a nonconjugated unsaturated nonhydroxylated aliphatic acid having from ten to twenty-four carbon atoms in the carbon chain is obtained with maleic anhydride or the like.

It will 01' course be apparent that an attempt to condense maleic anhydride or the like with a nonconjugated unsaturated hydroxylated aliphatic acid having from ten to twenty-four carbon atoms in the carbon chain, or a salt or ester thereof, will result in esterification between the acidic group of maleic anhydride and the hydroxyl group or groups in the aliphatic acid, salt or ester. Condensation between themaleic anhydride or the like and the carbon chain of the hydroxylated aliphatic acid, salt, or ester; will only take place after esteriflcation is complete,

and in case maleic anhydride or the like in excess of that consumed by the esterification is present in contact with'the esterified hydroxylated aliphatic acid, salt or ester under the proper conditions.

The esterification of course produces a change in properties, and the condensation product of a hydroxylated aliphatic acid, salt or ester can ated aliphatic acid having from ten to twentyfour carbon atoms in the carbon chain, due to thechange in properties caused by esteriflcation, and due to the difliculty of decomposing the ester, the claims have generally been drawn to exclude hydroxylated aliphatic acids, salts and esters. This means that such acids, salts and'esters are not suificiently hydroxylated to interfere with the condensation by esterification. Oils which are polymerized by blowing with air are usually hydroxylated.

In those cases where the claims do not exclude hydroxylated aliphatic acids, salts and esters, it will be understood that more than mere esterification is intendedthere should be condensation at a point of unsaturation on the carbon chain of the acid, salt or ester.

When reference is made to the maleic grouping in condensable form, it will be understood that'it is intended to designate maleic anhydride, a substance yielding maleic anhydride or a maleic ester or similar compound which is capable of condensing to enter the carbon chain of a nonconjugated unsaturated nonhydroxylated aliphatic compound having from ten to twenty-four carbon atoms in the carbon chain. A maleic condensation product may be obtained from any such compound having the maleic grouping, preferably maleic anhydride.

As will be later explained in considerable detail, the presence of the acid or acid anhydride radical in the condensation product is distinctly advantageous, because of the reactions of which the acid or acid anhydride radical is capable and the uses to which such reactions may be put.

A wide'variety of nonconjugated unsaturated nonhydroxylated carbon chain compounds having from ten to twenty-four carbon atoms in the carbon chain may be employed. Esters of fatty acids with mono-, dior poly-hydric alcohols, for example glyceryl or glycol esters, are Particularly desirable. The free fatty acids may also be used. Salts of the fatty acids (soaps) may likewise be employed.

When reference is made to the length of the carbon chain as being from ten to twenty-four carbon atoms, it is intended to include compounds having ten carbon atoms, twenty-four carbon atoms' or any intermediate number of carbon atoms in the chain. The reference to the length of the carbon chain applies to the carbon chain of the acid. A glyceride, for example, contains three such carbon chains united to a glyceryl group.

As examples of the type of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in the carbon chain which I may use, I suggest oleic, linolic, linoleic, clupanodonic and undecylenic.

The-esters of the nonhydroxylated fatty acids 7.

may be either glyceryl esters, which form oils such as corn, olive (triolein) cottonseed, peanut, linseed, sunflower, saillower, perilla, hemp seed, walnut seed, soya bean, rape seed, tomato seed,

neats-foot, lard, codliver, cod, burbet, salmon,

menhaden, and many others, all nonconjugated unsaturated nonhydroxylated fatty oils; or esters of other alcohols, for example glycol esters. It will furthermore be understood that mixtures of various esters, or of the esters and the free fatty acids, or of salts of the acids, may be employed if desired.

When .I refer to the grouping of a nonconjugated unsaturated nonhydroxylated aliphatic acid having from ten to twenty-four carbon atoms in the carbon chain, I mean to include the acid, and compounds of the acid such as esters of the acid, whether with mono-, dior polyhydric-alcohols, and salts of the acid. I do not include herein hydroxylated aliphatic acids, oils, etc., because, while the condensation of my invention may in certain cases be obtained with them, special precautions must be taken because of the tendency of hydroxylated fatty acids, oils,

etc., to esterify and gel. Typical hydroxylated fatty oils are castor oil and cashew nut shell oil. The question of whether the free acid or the ester or the salt is used is immaterial from the standpoint of the condensation reaction because the condensation reaction with the maleic anhydride appearsto involve the carbon chain at an intermediate point between its ends, rather than the carboxyl group or neutralized carboxyl group at the end of the chain. Of course, the character of the product will vary depending upon whether the acid, ester or salt is used.

In the condensation, I may desirably employ one molecular equivalent of nonconjugated unsaturated nonhydroxylated acid or the like to one molecular equivalent of maleic anhydride or the like and subject the mixture to a temperature of between 150 C. and 300 C. (more desirably between 180 C. and 260 C.) and preferably also to high pressure to facilitate the reaction. Pressure may desirably be applied by simply confining the reaction components between the walls of some vessel such as a pressure autoclave and then heating the reaction components. Pressure may also be applied in any other suitable way, as by pumping the reaction components into the vessel or introducing an inert gas under pressure. I have used pressures upto 300 pounds per square inch with success. Of course the desirable pressure will vary with the individual reaction.

A suitable catalyst may be used to accelerate the reaction and to increase the yield. I do not, however, find that a catalyst is necessary.

The condensation reaction may be carried out in the presence of suitable-solvents, although this is not usually necessary.

In ordinary practice I prefer not to use sufficient maleic anhydride or the like to saturate all of the double bonds in the fatty acid or fatty oil, etc., having from ten to twenty-four carbon atoms in the carbon chain. The condensation product thus ordinarily has an iodine value. Generally it is 3ufiicient to saturate one-sixth to onethird of the double bonds in the fatty acid, fatty oil, etc. Thus in olive oil one-third of the double bonds (one) is ordinarily saturated, and in linseed oil one-sixth (one). But in individual cases it may be desirable to satisfy more ethylene linkages in the fatty acid or fatty oil, and even to completely saturate them. To saturate all of the linseed oil, six molecular ethylene linkages 'in equivalents of maleic anhydride or the like are caused to react with one molecular equivalent of linseed oil.

Examples 1 to 4 given below, clearly indicate the way in which my improved condensation product is obtained.

EXAMPLE 1 Ina pressure autoclave, 180 parts by weight of raw alkali-refined linseed oil are mixed with 20 parts by weight of maleic anhydride. The temperature is maintained at from 250 C. to 260 C. for one hour,'a pressure of about 30 pounds per square inch developing. The reaction may be obtained satisfactorily at 150 C., but is much slower at this low temperature, and the temperature may be raised to as much as 300 C., but a high temperature may cause some difficulty due to carbonization. After cooling, the reaction product is removed from the autoclave. The condensation product is slightly darker and more viscous than the original linseed oil. It is soluble in acetone,

Into a three-neck flask, equipped with a thermometer, mechanical stirrer and reflux condenser, 200 parts by weight of distilled oleic acid and 60 parts vby weight of maleic anhydride are placed and heat is applied until the temperature of the mixture reaches 180 C.

The temperature is gradually raised from 180 C. to 250 C. over a period of one hour, during which time the amount of condensed maleic anhydride progressively diminshes. The temperature is maintained at 250 C. to 260 C. until no more maleic anhydride appears to condense. The temperatures given are those found best for carrying out the reaction, although temperatures between 150 C. and 300 C. may be used.

The condensation product is soluble in ethyl alcohol, ether, xylene, carbon tetrachloride and solutions of nitrocellulose, but is substantially insoluble in petroleum hydrocarbons and fatty oils.

EXAMPLE 3 To 180 parts by weight of linseed oil are added 25 parts by weight of citraconic anhydride (a substituted maleic anhydride) and the mixture is heated in a three-neck flask, equipped with a reflux condenser, at about 250 C. for about threequarters of an hour. At the end of this period, no further citraconic anhydride appears to condense, indicating completion of the reaction. As a precaution, heating is continued for about 15 minutes longer. The reaction product is less viscous than the maleic condensation product of linseed oil obtained in Example 1, but has the same properties otherwise.

ExAm'Ln 4 A mixture of 900 parts by weight of linseed oil and 112 parts by weight of acid methyl maleate (a maleic half ester) re heated under pressure at about 250 C. for bout two hours. If neutralized with an alkali, the reaction product forms anexcellent dispersing agent as later explained.

My novel condensation product may be made with nonconjugated unsaturated nonhydroxylated drying, semidrying or nondrying fatty oils having from ten to twenty-four carbon atoms in the carbon chain, or mixtures of the same, and

the characteristics of the product are, to some extent, dependent upon the character of the oils or the like employed in the reaction. In certain of the claims the oil is described by its chemical ingredients as predominantly consisting of glycerides of linoleic and oleicacids. When nonconjugated unsaturated nonhydroxylated drying oils are caused to react with maleic anhydride or the like, the products dry in the air at ordinary temperatures to form hard dry films whether or not driers are used. Likewise, the condensation products of nonconjugated unsaturated nonhydroxylated drying oils generally exhibit thermohardening properties, being convertible at '70 C.

to 80 C., for example into hard resistant varnishlike films in short periods of time. Where nonconjugated unsaturated nonhydroxylated semidrying oils such as sunflower, soya, saiilower, and other similar oils are caused to react with maleic anhydride or the like, the condensation products do not dry so readily as the condensation products obtained from the drying oils. An example of the drying behavior of the condensation product obtained by Example 1 is as follows:

EXAMPLE 5 A 1:1 xylene solution of the reaction product obtained in Example 1 to which soluble driers are added to the extent of 0.03% of cobalt, 0.05% of manganese and 0.5% of lead, for example in the form of linoleates or resinates, dries to a hard film at room temperature in about five hours and may be stoved to a hard film at 80 C. in about one and one-half hours. The film produced is not acted upon by water, ethyl alcohol, benzine, or xylene.

It is thus evident that the invention permits of the direct production of thermo-hardening and air-drying lacquers, varnishes, etc.

Without limiting myself to any exact structure for the condensation product, it would appear that the condensation product is an addition product at a double bond in the carbon chain of the nonconjugated unsaturated nonhydroxylated fatty acid or the like to the maleic anhydride or the like. For example, if linolenic acid reacts with maleic anhydride, the first stage in the reaction appears to be in general as follows. 01 course if enough maleic anhydride be present,

the same reaction will take place at each double bond inthe linolenic acid.

OH|CH;CH=OHCHiCH=CHCHzOH=OH(CH:)-/COOH+ O Maleic condensatioglgroduct oilinolenlc The iodine value of the condensation product confirms the above formula, and indicates that the ethylene linkage of the maleic anhydride or the like has been lost during condensation. It should be noted that one of the double bonds in linolenic acid and the ethylene linkage in maleic where X and Y are chains of carbon atoms without conjugated double bonds, the length of carbon chain from X to Y, inclusive is between ten and twenty-four carbon atoms, and Z is .oneofthe group consisting of hydrogen, metals and esters.

As a working hypothesis, itwould seem that the structural formula which results from the reaction of the present invention may possibly be ex-,

pressed in more simplified form as where the straight carbon chain is between ten and twenty-four carbon atoms in length and the terminus-U is one of the group consisting of aliphatic acids, salts thereof and esters thereof.

The reaction above will be modified in well known manner if a glyceryl ester of linolenic acid instead of linolenic acid be used, or if some other nonconjugated unsaturated nonhydroxylated aliphatic acid having between ten and twenty-four carbon atoms in the carbon chain be employed.

It should be noted that the maleic anhydride condensation product of linolenic acid or any similar acid has a. carboxyl group capable of reacting at the end of the linolenic or other similar carbon chain, and also an olefinic acid group capable of reacting. The condensation will take place notwithstanding that both of these groups have been esterified before the condensation reaction, but the presence of the unesterifled polarreactive groups is of great advantage for many purposes as later explained.

When maleic acid or a substance yielding maleic acid is condensed with a nonconjugated unsaturated nonhydroxylated fatty acid or the like, it appears to change to maleic anhydride and the maleic anhydride condensation product results.

Recondensatz'on The condensation reaction between maleic anhydride or the like and a nonconjugated unsaturated nonhydroxylated aliphatic acid or the like having from ten to twenty-four carbon atoms in its carbon chain has been described in general.

It is possible to recondense the maleic anhydride condensation product of a nonconjugated unsaturated nonhydroxylated aliphatic acid or the like to produce more complex recondensed products. For example, the condensation product of maleic anhydride or the like and a nonconjugated unsaturated nonhydroxylated aliphatic acid or the like having from ten to twenty-four carbon atoms in its carbon chain may be condensed with a phenoheither with or without a condensing agent such as hexamethylenetetramine. Likewise, the maleic condensation may be brought about in the presence of a phenol and aldehyde, with or without a condensing agent 7 such as hexamethylenetetraminea As is well known, henols and aldehydes themselves possess a tendency to condense, and, when the maleic condensation product of a nonconiugated unsaturated. nonhydroxylated aliphatic acid or the like is present, a complex recondensation takes place between the alkyl substituted. olefinic condensation product, the phenol and the aldehyde. Recondensation proceeds more satisfactorily when the condensation product contains an acid group.

On the other hand, other reactive resin-forming or resinii'ying substances maybeused toreplace part of the maleic condensation product in the recondensation.- For example, a mixture 01' the maleic condensation product of a nonconiugated unsaturated nonhydroxylated aliphatic acid or the like'having from ten to twenty-four carbon atoms \in its carbon chain with benzoyl *benzoic acid (or other reactive resinifying or resindorming substances) may be condensed with a phenol or mixture of a-phenol'and analdehyde, with with out the a'ssistanceof a con densing agent'such as hexamethyl'enetetramine.

The recondensation product obtained by using the maleic condensation product of a nonconjugated unsaturated nonhydroxylated aliphatic acid or the like having'i'rom ten; to twenty-four carbon atoms in its carbon chain and some other substance or substances capable o1 undergoing condensation is socomplex that even an approximate statement of its structureat the present time is not to be attempted. For the purpose of illustration, however, I give a specific example 01' a relatively simple recondensation, with knowledge that persons skilled in the art can readily devise other recondensations to suit particular needs.

Exmtz 6 temperature is held at 200 C. until the mass becomes almost solid. 7

The recondensation product is a resinous mass, soluble in xylene, which, in the presence of metallic driers, may be stoved to give a hard film, for example at 80 'C. The reaction as described above may be carried out with a great variety of the substances or the types given, and with varivoils quantities and conditions, the change of which is within the skill of a routine experimenter.

' Acid reactions I As notedabove, an acid group 01' the condensa tion' product is capable of a widevariety of reactions to produce desirable products of various kinds. For example, very satisfactory oil-soluble 'driers may be manufactured by causing the condensation product ofmaleic anhydride and a nonconjugated unsaturated nonhydroxylated aliphatic 'acid or the like having from ten to twenty-iour carbon atoms in the carbon chain, particularly a glyceride of such acid; to react with a metallic oxide, hydroxide, carbonate or other simi- A desirable feature of my invention is that the condensation product oi. maleic anhydride with nonconjugated unsaturated nonhydroxylated drying oils forms an excellent vehicle or ingredient for a vehicle'for paints, etc. This reacts with metallic oxides and hydroxides, and with carbonates and acetates in the presence of water, to form a drier which is chemically combined with the vehicle. Such a drier is made by adding a small percentage of lead oxide to the maleic anhydride condensation product of linseed oil (for example, enought to introduce of lead into the condensation product).

Esterification of the acid group is frequently desirable. The alcohol used may be either aliphatic or aromatic and either mono-, dior polyhydric.

ExaurLn 7 A typical case of esterification is exhibited when parts by weight of the viscous oil obtained by the interaction of maleic anhydrideand linseed oil, as described for instance in Example 1, are mixed with 1.6 parts by weight of ethylene glycol and the mixture is maintained at about 180 C, until thereaction ceases. A 1:1 xylene solution of the reaction product, when treated with a suitable quantity of metallic driers, as described for instance in Example 5, dries at room temperature to a hard film in a somewhat shorter time than that required for linseed oil and, when stoved at 80 C., gives a hard film in about one and one-half hours. The film is not attacked by water, alcohol or xylene.

In the above reaction the ethylene glycol neutralizes the acid anhydride and forms an ester. Of course, if the starting material is the condensation product oi'linolenic acid instead of its glyceride, esterification takes place at the carboxyl group aswell as at the acid anhydride group, as the condensation product is then polarreactive at two distinct parts of the molecule.

The polar-reactive ,quality of the acid group in maleic anhydride isiofgreat importance when its condensation product with a nonconjugated unsaturated nonhydroxylated aliphatic acid or the like having from ten to twenty-four carbon atoms inits carbon chain is used as a metal coating. In this instance the acid group acts upon the metal which is coated and produces very tenacious adherence of the film. This makesthe 'maleic anhydride condensation product of a nonconjugated unsaturated nonhydroxylated allphatic acid or oilor the like having from ten to twenty-four carbon atoms in its carbon chain very desirable as a base or priming coat. The suitability of the maleic anhydride condensation product of a noncon jugated unsaturated non- 1 hydroxylated acid or the like for primingorba-se and ethyl acetate) are completely miscible with coat purposes is increased whennitrocellulosc lacquers are employed-for a subsequent coat or coats, because nitrocellulosesolutions (for example, nitrocellulose dissolved in ethyl alcohol the maleic anhydride condensation product and firm adherence between the condensation product coat and the nitrocellulose coat .or coats is thus obtained. The advantage of thecondensation product as a base for nitrocellulose is present It will be understood,

lacquers, such as maleic condensation product paints orlacquers, or paints or lacquers based .upon; drying oils or mixtures of these.-- I

v EXAMPLE 8 v rampa ts by weight of the viscous oil on tained bytheinteraction of linseed oil and maleic anhydride as described for instance in Example 1,.solubledrier's are addedto, the extent of about v0.93% cobalt, 0.05% manganese, and 0.5% lead l inthe form of, linoleates or resinates. One. half of a polished .zinc plate is coated with a 1:1 xylene solution of'the product just described and the film is stoved at 80C. for one and one-half -hours.l-

1 'I'he film adheres very tenaciously to the metall'i'c surface, and, if the film is removed by boiling acetone, the surface to which the film was attached shows adecided etching eii'ect while the surfaceofthe zinc which was: not coated isunaflected. The etching effect appears to be due to the'action of the acid anhydride radical in the maleic condensation product of: linseed oil on thezinc 2-;

Application of a film of nitrocellulose lacquer to :the films of the maleic condensation product of linseed oil results in excellent adherence of the nitrocellulose film to the maleic condensation product Ifilm and of the maleic' condensation product film to. the metal.

, The property of firm adherence-to metal surfaces is exhibited with all of the ordinary structural andcoating metals, such as zinc, tin, lead, copper, iron, aluminium, chromium, nickel, cadmium, etc., and their various alloys, such as steel, michrome, brass, bronze, zinc die-cast metal, etc. The maleic anhydride condensation product of linseed oil dries much more quickly on copper than linseed oil, probably because the copper salt of the condensation product acts as a drier; Adherence to the copper is extremely firm.

My novel condensation product is very satisfactory for use with nitrocellulose solutions in lacquers, etc., The proportions need not be restricted, although I have found that 20% to 50% of nitrocellulose solution and to 50% of "condenseddrying oil make a suitable vehicle.

The polar-reactive groups in the condensed drying .oil give firm adherence.

I have observed that the condensation prodnot of maleic anhydride and a nonconjugated unsaturated nonhydroxylated drying oiladheres very firmly to wood and leather, doubtless due to the presence of the polar-reactive group. I therefore recommend this product as an improved -paint vehicle, or patent leather coating substance.

An improved varnish or the like may be made by gelling a mixture of natural or synthetic resins cooling the ,mixture to 0.} partsby or other polyhydric alcohol, and the reaction 21-4 ,ieeaa and themaleic anhydrideor equivalent condensation product of a drying oil, then incorporating the gelled-condensation product with a natural .or synthetic resin; and dissolving in a solvent.

The gelling may be accomplishedby heating of 5 the condensation product.

Exlmrna 9 parts by weight of ester gum. are addedan'd the 1,

mixture is heated until it becomes uniform- After 15 weight of petroleum spirits, containing drier, are a added.

The varnish thus bunnies dries as a claim film. I. Wood rosin, cumar, and f run copal may be c1 used successfully in place of theester gum.

The condensation product of the invention is remarkablein its ability to dissolve moderately run, hard copal, cuman, hard Bakelite and durez, which are not soluble in the ordinary solseed oil, f orexai'nple.

It is pcssibletc manufacturefan improved varnish or the like from the maleic anhydride or equivalent condensation product of a drying oil, which is caused to react with glycerine,

product incorporated with a resin, preferably rosin. This mixture may be heated to the required varnish viscosity and then thinned with common organic solvents.

I Exsinrna it) I Heat together 100 'partsby weight oi the maleic anhydride condensation product of linseed oil as obtained in Example 1, and 11 parts by weight of glycerine at 230 C. until a drop of the reaction mixture remains clear on cold metal. Then add to the reaction mixture 60 parts by weight of wood rosin'and heat at 285 C. for 45 minutes.

Very desirable colored varnishes and lacquers rnay be obtained by using the condensation prodnot of maleic anhydride or the like and a drying oil, with orv without the addition. of a-synthetic or natural resin, together with a basic dyestuif. The acidic group of the maleic anhydride conden- I sation product appears to combine with the basic groupof the dyestufif. The reaction may be brought about directly or in the presence of a suitable solvent. J

; I .EXAMFLE 11 A solution of one part by Weight of Victoria blue dye base in ten parts by weight of hot toluene is mixed with' lfiii parts by Weight of the maleic anhydride linseed oil condensation product of 70 Example 1. The blue color of the dye is developed by the acid anhydridegroup of the condensation product. By the addition of driers, the product may be dried to a transparent color-ed film.

Some of the basic dyestufis which may be is preferable.

masses for example instead of Victoria blue to produce colored lacquers are:

Red Magenta Safranine Rhodamine Toluidine red Violet Crystal violet Paraphenylene violet Blue Methylene blue Victoria blue (already mentioned Night blue Paraphenylene blue Yellow Leather yellow Chrysoidine Green Malachite green Brilliant green Azine green Brown Bismark brown A very desirable feature of. my invention is the ability to produce dispersing agents for dispersing solids and emulsifying liquids. I have discovered that such a desirable dispersing agent may be obtained by producing a soluble salt, acid salt or salt-ester of the condensation product oi maleic anhydride or the like and a nonconjugated unsaturated nonhydroxylated fatty acid or the like having from ten to twentyfour carbon atoms in its carbon chain. For

dispersing purposes the salt-ester of the maleic condensation product of a nonconjugated unsaturated nonhydroxylated nondrying fatty oil Experimenting upon the maleic .anhydride condensation product of a nonconjugated'um saturated nonhydroxyiated fatty oil having from ten to twenty-four carbon atoms in its carbon chain, I have found that the completed salt, in which the maleic grouping is combined with carbonyl groups neutralized by an alkali metal base, for instance potassium or sodium hydroxide, or an organic base such as triethylamine, is a satisfactory dispersing agent. The acid salt, in which one carboxyl group is not neutralized and another is neutralized by an alkali metal base or organic base, is likewise a satisfactory dispersing agent. Also, the salt-ester is satisfactory. The completed ester is not a good dispersing agent.

When reference is made in the claims to salts in the present connection, it is intended to include completed salts, acid salts andsalt-esters. The base usedin forming the soluble salt may be an alkali metal base or an organic base.

In producing my desirable dispersing'agent, I preferably esteriiy the maleic condensation prod" not with the theoretical quantity of an aliphatic or aromatic alcohol to produce an acid ester and then neutralize the acid ester with a suitable base or alkali to form a soluble salt-ester. The resultant product is a water-soluble oil which may be mixed with other oils to produce an emulsion. Emulsions made in this wayhave been found to be very stable and very neutral. Such oil emulsions may be used to advantage instead of sulphonated oil emulsions because the stability, wettability, solubility and dispersive power of the dispersing agent obtained by my invention is greater than in the case of sule phonated oils. Emulsions produced by my dispersing agents have the further advantage over sulphonated oil emulsions that they are not decomposed, and particularly do not liberate an acid group as do the sulphonated oils, which liberate sulphuric acid upon decomposition.

Large quantities of sulphonated oils are now used for dispersing, wetting and softening agents in the textile, leather, paper, plaster and cement industries. My improved product is according to tests by me superior to the commonly used sulphonated oils for use as a dispersing, wetting and softening agent in these and other industries. In the textile field, my product may be used in delusteringrayon, for example:

Using my novel dispersing agents, I have produced very satisfactory dispersions of 'carnauba wax in water, of petroleum hydrocarbdns in water and of many vegetable oils, such as linseed, olive, neats foot, caster, etc., in'water. T

My new dispersing agent is very desirable'as' a bodying agent in the making of polished-cutting fiuids and cosmetics. There are of course many other uses too numerous to mention-.. ,-I

EXAMPLE 12 To 50 parts by weight of the viscousioil tained by the interaction of maleic anhydride and olive oil under conditions similar ,to those described for instance in Example 1;.( 1.-molecular equivalent of maleic anhydride to 1 molecular equivalent of olive oil) are added 5 p rts by.

weight of is'oamyl alcohol and the ingredients are refluxed for one-half hour. Any suitable alcohol may be used for this esteriflcation, although the quantity of alcohol used will of course depend upon the particular alcohol. The reaction produces an acid ester. r

The product is neutralized with thetheoretical amount of a base, preferably sodiumgor potassium hydroxide in concentrated aqueous solution. The resultant oily product is miscible with water in all proportions and is likewise" miscible in all proportions petroleum hydrocarbons.

The neutralized acid ester as prepared above may be added to any suitable fatty oil or petroleum hydrocarbon to produce dispersion.

The acid ester may be added to the disperse phase before neutralization, and neutralization may be accomplished in the presence of the disperse phase.

with fatty oils and EXAMPLE 13 To a water-insoluble hydrocarbon, alcohol, or fatty oil, such as olive oil, castor oil, etc., or wax such as carnauba or candelilla, the soluble sa1t-ester of a nonconjugated unsaturated non hydroxylated fatty oil condensation product as prepared in Example 12 is added until the ester forms 20% of the mixture. This mixture is readily emulsified with water due to the presence of the water-soluble neutralized acid ester,

, sation product coats the pigment and when the very satisfactory as a wetting and softening agent for the textile, leather, and paper industries.

An ester of the condensation product may be hydrolyzed or partially hydrolyzed and. then neutralized to produce a dispersing agent.

Paint There are a number of properties of the condensation product of maleic anhydride or the like with a drying oil such as linseed oil which specially suit this condensation product for use as a paint vehicle.

Hardness.-When the condensation product as obtained in Example 1 dries in a film, the film has been found to have a hardness greater than the film produced under similar conditions using raw linseed oil. A small amount, for instance 1% to 3%, of the condensation product obtained in Example 1, added to the raw linseed oil, greatly increases the resistance of the resultant film to accelerated weathering tests. ,The paint whose vehicle contains 3% of the condensation product above referred to shows less pitting and chipping than a paint which is exactly similarexcept for the absence of the condensation product.

Water resistance-A thoroughly dried film of the condensation product obtained in Example 1 'has been found to have a far superior resistance both to cold and boiling water than a similar film of the drying oil from which the condensation product was made, for instance linseed oil. V If a dry film of raw linseed oil is placed in distilled water at room temperature, a foggy appearance develops on the surface within about forty-eight hours. A dry film of the condensation product exposed to distilled water under similar conditions shows no fogging after one ,week of exposure.

When subjected to boiling water, the dry film of raw linseed oil applied to a glass plate comes off within a few seconds while the dry film of the condensation product of Example 1 applied to glass under similar conditions resists for about two minutes before it peels off.

Wettabz'lity.-The mixing of pigment with vehicle can be greatly facilitated by virtue of the superior wettability of the condensation product of the present invention for pigment. The condensation product obtained in Example 1, for instance, has a-preferential adhesion to pigment. This may be employed by mixing a small quan-. tity (say 1% or 3% based on the total weight of vehicle), of the condensation product of Example 1 with the pigment and then adding the remainder of the vehicle which may simply be raw linseed oil. The initial addition of the condenraw linseed oil is subsequently added the mixing with the raw linseed oil is very readily accomplished. Superior mixing is also obtained even though the condensation product and the raw linseed oil are mixed together before being incorporated with the pigment. The time required for mixing with a pigment, such as zinc oxide, is very much reduced. It is much easier to grind the pigment with the vehicle if a few percent of the condensation product of the present invention are included in the vehicle or preferably are added to the pigment before mixing with the main body of the vehicle.

SettZing.--The condensation product of the present invention increases the permanence of suspension of pigment in a vehicle. As little as 3% of the-condensation product of Example 1 incorporated in an ordinary linseed oil vehicle gave the following improvements in settling:

In the above scale 1 indicates no settling and 10 indicates maximum settling, With white lead pigment, the settling tendency was improved by 3% of the condensation product from 9+ to 6, while with zinc oxide the improvement was from 9+ to 3+. Even in lithopone and titanox paints, which have very little tendency to settle,

an improvement was noted. The decrease in settling tendency, due to the condensation product as obtained in Example 1, or other condensation product of the present invention, constitutes a marked improvement from the standpoint of packaging paint and also in obtaining an even mixing of the paint by the user after opening the can.

Superpigmented paint-A very beneficial effect of the condensation product is that it makes possible exceptional increases in the pigment contents of paints. Whereas ordinary commercial paint commonly has a pigment content of about 28% to 30%, it is possible to obtain a pigment content of 40% without difiiculty, by using the condensation product of the present invention (Example 1 for instance) as the vehicle or as an ingredient of the vehicle. A very desirable vehicle for such superpigmented paints may contain 15% of the condensation product of Example l with the remainder raw linseed oil. Such superpigmented paint may be applied with a brush with the-usual quantity of thinner and,

fiows without difliculty. The superpigmented paints produced as just explained have film strengths two to three times the film strengths of paints which have the ordinary quantities of pigments. The superpigmented paints are also markedly less responsive to ultra violet light.

The films of such superpigmented paints are denser'and of increased hiding power. Superpigmenting is advantageous in printing inks as wellv-as'in paints.

Leveling-Elie paint produced by the use of thecondensation product of the present invention as the vehicle or as an ingredient of the vehicle (for example 3% of the vehicle) has superior leveling properties. These. are so marked that where two paints arecomparedinuse, identicalexcept that one contains 3% of the condensation product of Example 1, it might be supposed by uninformed persons that the paint containing the condensation product was really enamel rather than paint because of the great smoothnessand the removal of brush marks.

caused bythefcondensation product. The leveling property would appear to be due to the dis-- product of maleio anhydr'ide or the like with a drying oil as made for instance-in Example 1 has controlled penetration properties. Expressed .erential adhesion to the pigment.

in other words, when a film containing said condensation product is painted in the ordinary manner as the priming coat on wood or other permeable material, the vehicle will not leave the pigment but .will penetrate only a few cells deep into the wood. In the ordinary paint using raw linseed oil alone as a vehicle, the vehicle will penetrate far into the wood leaving the pigment at the surface with a depleted vehicle content or without any vehicle. This is a frequent cause of failure of paint films. The reason for the controlled penetration of the condensation product of the present invention would appear to be pref- The conventional test for controlled penetration is painting an unglazed blotter and observing whether-the paint penetrates to the other side. In case the condensation product of the present invention is used as the vehicle, it is found that the vehicle remains with the pigment on the side painted, while linseed oil will leave the pigment and soak into the blotter, being observable on the other side. This feature has contributed to the successful test of the condensation product of the present invention as a priming coat.

It will immediately be evident to persons familiar with the art that the disclosure of the present invention is of wide utility in a number of diversified industries, as it provides a means of altering the properties of any one of a wide variety of commercially used oils to fit them to several new needs. For example, it is possible to obtain greatly increased viscosity.

A very desirable property of the condensation product of maleic anhydride or the like with drying oils is that the viscosity is only slightly increased by virtue of the condensation.v It is, however, possible to body the condensation product of maleic anhydride or the like with a drying oil such as linseed oil, either by blowing or heating or both, either in the presence of a drier or without a drier. Such bodied condensation product may be used in the paint, lacquer and varnish industry, and for related purposes.

EXAMPLE 14 Heat parts by weight of the condensation product of maleic anhydride and linseed oil as obtained in Example 1 to 305 C. and maintain it at this temperature with constant stirring until the viscosity reaches the desired value. The viscosity of the condensation product increases very rapidly at this temperature, and any required viscosity short of the gel stages may be obtained. The reaction period is generally less than one hour.

The condensation product obtained as above may be heated until a one-half inch string pours from cold metal. This condensation product is then cut with'an equal weight of raw linseed oil. Seven parts by weight of the mixture is added to a paint containing 225 parts by weight of white lead paste, 40 parts by weight of raw linseed oil and 7 parts by weight of thinner plus drier. The final composition of the paint is 28% pigment by volume, with the vehicle containing 10% thinner by weight. This paint shows greatly improved,

viscosity, markedly superiorpigment suspension and greatly improved levelling properties.

The maleic anhydride condensation product of linseed oil obtained in Example 1 may be blown at C. to produce the same viscosity as that described in Example 14 above, and the blown condensation product may be used in the same general way. The blown-bodied condensation products are superior in color to the heat-bodied condensation products of the present invention.

I can increase the wettability of oils to pigments, with consequent improvement in the mixing, grinding and leveling properties. It is also possible to increase tremendously the property of a film of firm adherence to metal and of firm adherence to special lacquer films which are subsequently applied. It is also possible to render the product soluble in water and to produce stable dispersions.

I believe that I am the firstto discover that maleic anhydride or the like will condense with the carbon chain of a nonconjugated unsaturated nonhydroxylated aliphatic acid, nonhydroxylated ester, nonhydroxylated salt, etc. having from ten to twenty-four carbon atoms in the carbon chain. I frequently refer to such nonconjugated unsaturated nonhydroxylated aliphatic acids, nonhydroxylated esters, nonhydroxylated salts, etc., as nonconjugated unsaturated nonhydroxylated fatty acid compounds, or compounds having the fatty acid grouping. For different compounds, some variations in desirable reaction temperatures and pressures will be found.

Wherever I refer herein to resin-forming substances I mean to include resinifying substances also, and when I refer to resinifying substances, I

likewise mean to include resin-forming substances.

Throughout the specification and claims, where I refer to nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in the carbon chain, or nonhydroxylated salts or nonhydroxylated esters thereof, I mean such acids, salts or esters as are unoxidized or nonpolymerized or not sulficiently oxidized or polymerized to interfere with the reactions disclosed herein. Thus, in referring to linseed oil, I mean the product generally known as such, raw or refined, and not linseed oil sufiiciently oxidized or polymerized to prevent or seriously interfere with the formation of a condensation product at a double bond. In other words, I do not intend to exclude others from mere esteriflcation of oxidized or polymerized fatty oils by maleic anhydride.

Many of the fish oils contain varying percentages of fatty alcohols, which will of course react with maleic anhydride to form esters. The esterifled fatty alcohols may be allowed to remain in the condensation product, or the alcohols may be removed before condensation takes place.

It will be evident that the condensation product of my inventionmay be oxidized subsequent to condensation.

Where reference is made to poly-hydric alcohols, it is intended to include di-hydric alcohols. Reference to acids is intended to include acid anhydrides and half esters of acids. Reference to esters is intended to include partially completed esters such as half esters;

In view of my invention and disclosure variations and modifications to meet individual whim or particular need will doubtless become evident to others skilled in the art, to obtain all or part of the benefits of my invention without copying the exact process or product described, and I, therefore, claim all such in so far as they fall within the reasonable spirit and scope of my invention. I

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. The process of forming a condensation product, which comprises reacting one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids havingless than ten carbon atoms in their carbon chains and maleic esters, at a double bond in the carbon chain of one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, at a temperature in excess of 150 C., the reaction being wholly between the one of the first group and the one of the second group and continuing the heating until a substantial quantity of the one of the first group is combined at an intermediate point in the carbon chain in the one of the second group.

2. The process of forming a condensation product, which comprises reacting one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, at a double bond in the carbon chain of one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, at a temperature not less than 150 C. and in excess of the ordinary boiling point of the one of the first group with return condensation and for a time sufficient to produce a substantial amount of the condensation product, the reaction being wholly between the one of the first group and the one of the second group.

3. The process of forming a condensation product, which comprises reacting one of the group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, with an unsaturated linkage of an oil predominently consisting. of glycerides of linoleic and oleic acids at a temperature in excess of C. and continuing the heating until a substantial quantity of the one of the group is combined at an intermediate point in the carbon chain of the fatty acid of the oil, the reaction being wholly between the one of the group and the oil.

4. The process of forming a condensation product, which comprises reacting one of the group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, with an unsaturated linkage of an oil predominantly consisting of glycerides of linoleic and oleic acids at a temperature not less than 150 C. and in excess of the ordinary boiling point of the one of the group with return condensation and for a time sufflcient to produce a substantial amount of the condensation product, the reaction being wholly between the one of the group and the oil.

5. The process of forming a condensation product, which comprises heating a mixture of one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, aikyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters,

with one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acidshaving from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, to a temperature between 150 C and 300 C., the reaction being wholly between the one of the first group and the one of the second group, and continuing the heating untila substantial quantity 0f the one of the first group is combined at an intermediate point in the carbon chain in the one of the second group and in the presence of no substantial excess of the one of the first group over the quantity necessary to saturate all double bonds in the one of the second group. a

6. The process of forming a condensation product, which comprises reacting one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, at a point of unsaturation in the carbon chain of one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, at a temperature not less than 150 C. and in excess of the ordinary boiling point of the one of the first group with return condensation and for a time sufilcient to produce a substantial amount of the condensa-' tion product and in proportions which saturate less than all of the double bonds in said one of the second group, the reaction being wholly between the one of the first group and the one of the second group.

7. The process of forming a condensation product, which comprises reacting one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, with one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, at a temperature between 150 C. and 300 C., the

reaction-being wholly between the one of the first group and the one of the second group and continuing the heating until a substantial quantity of the one of the first group is combined at an intermediate point in the carbon chain in the one of the second group and in proportions of about one molecular equivalent of the one of the first group to one molecular equivalent of the one of the second group.

8. The process of forming a condensation product, which comprises reacting one of the first group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains'and maleic esters, with one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chain, nonhydroxylated salts and nonhydroxylated esters thereof, at a temperature not less than 150 C. and in excess of the ordinary boiling point of the one of the first group with return condensation and for a time suflicient to produce a substantial amount of the" condensation product and in proportions of about onemolecular equivalent of the one of the first group to one molecular equivalent of the one of the second group, the reaction being wholly between the one of the first group and the one of the second group.

9. The process of making a condensation product, which comprises applying heat and pressure above atmospheric to a mixture of one of the first group consisting of maieic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maieic acids having less than ten carbon atoms in their carbon chains and maieic esters,- with one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts'and nonhydroxylated esters thereof, at a temperature between 150 C. and 300 C., and continuing the heating until a substantial quantity of the one of the first group is combined at an intermediate point in the carbon chain in the one of the second group and in the presence of no substantial excess of the one of the first group over the quantity necessary to saturate all double bonds in the one of the second group, the reaction being wholly between the one of the first group and the one of the second group.

10. The process of forming a condensation product, which comprises reacting maieic anhydride at a point of unsaturation in the carbon chain or a drying oil predominantly consisting of glycerides of linoleic and oleic acids at a temperature between 150 C. and 300 C., the reaction being wholly between the maieic anhydride and the oil and continuing the heating until a substantial quantity of the maleic anhydride is combined at an intermediate point in the carbon chain of the fatty acid of the oil.

11. The process 01. forming a condensation product, which comprises reacting maieic anhydride at a point of unsaturation in the carbon chain of a drying oil predominantly consisting of glycerides of linoleic and oleic acids at a. temperature in excess of the ordinary boiling point of maleic anhydride with return condensation and for a time sufiicient to produce a substantial amount of the condensation product, the reaction being wholly between the maleic anhydride and the oil.

12. The process of producing ,a drying oil of increased utility for the paint, varnish and lacquer industry and the like, which comprises reacting one of the group consisting of maieic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maieic acids having less than ten carbon atoms in their carbon chains and maieic esters, with a nonconjugated unsaturated nonhydroxylated drying oil having from ten to twenty-four carbon atoms in the carbon chain at a temperature in excess of 150 C., the reaction being wholly between the one of the group and the oil and continuing the heating until a substantial quantity of the one of the group is combined at an intermediate point in the carbon chain of the fatty acid of the oil, and bodying the condensation product by blowing.

13. The process of producing a drying oil of increased utility for the paint, varnish and lacquer industry and the like. which comprises reacting one of the group consisting of maieic acid and its'anhydride, compounds which yield the same under the conditions of the reaction, allqrl- -substituted maieic acids having less than ten 14. The process of forming a condensation product, which comprises reacting maieic anhydride with linseed oil at a temperature not less than 150 C. and in excess of the ordinary boiling point of the maleic anhydride with return condensation and for a time sufllcient to produce a substantial amount of the condensation prodnot, the reaction being wholly between the maleic anhydride and the oil. I

15. A condensation product comprising one of the first group consisting of maieic acid and its anhydride, compounds which yield the same on der the conditions of the reaction, alkyl-substituted maieic acids having less than ten carbon atoms in their carbon chains and maieic esters, combined at an unsaturated linkage with one of the second group consisting of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonhydroxylated salts and nonhydroxylated esters thereof, by heating at a temperature in excess of 15o C. and continuing the heating until a substantial quantity or? the one of the first group is combined at an inter mediate point in the carbon chain in the one or" the second group, the quantity of said one of'the first group being not substantially in excess of that required to saturate said one of the second group and the reaction being wholly between the one of the first group and the one of the second group.

16. A condensation product comprising one of the first group consisting of maieic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maieic acids having less than ten carbon atoms in their carbon chains and maieic esters, combined at an unsaturated linkage with one of the second group consisting of nonconjugated on saturated nonhydroxyiated aliphatic acids having from ten to twenty-four carbon atoms in their carbon chains, nonlwdroxylated salts and nonhydroxylated esters thereof, by heating at a temperature in excess of 150 C. and continuing the heating until a substantial quantity of the one of the first group is combined at an intermediate point in the carbon chain in the one of the second group, and in the proportions of one molecular equivalent of the one of said first group to one molecular equivalent of said one of the second group, the reaction being wholly between the one of the first group and the one of the second group.

17. A condensation product comprising one of the first group consisting of maieic acid and its anhydride, compounds which yield the same un der the conditions of the reaction, aikyi subeti tuted maleic acids having less than ten carbon atoms in their carbon chains aid maieic esters, combined at an unsaturated linkage with one of the second group consisting of nonconjugated un saturated nonhydroxylated aliphatic acids having from ten to twenty-tour carbon atoms in their carbon chains, nonhydroxyiated salts and nonhydroxylated esters thereof, by heating at a temperature between l50 C. and 300 C, the reaction being wholly between the one of the first group and the one of the second group, and continuing the heating until a substantial quantity of the one of the first group is combined at an intermediate point in the' carbon chain in the one of the second group and in proportions which substantially completely saturate the double bonds in said nonconjugated unsaturated aliphatic compound without substantial excess.

l8. A condensation product comprising the product of reaction of one of the group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their ca bon chains and maleic esters, at a point of unsaturation of the carbon chain of an oil predominant- 13] consisting of glycerides of linoleic' and oleic acids, at a temperature between 150 C. and 300 C., the reaction being wholly between the one of the group and the oil, and continuing the heating until a substantial quantity of the one of the group is combined at an intermediate point in the carbon chain of the fatty acid of the oil.

19-. In a paint vehicle, a liquid condensation product of one of the group consisting of maleic acid and its'anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maieic esters, ata point of unsaturation of the carbon chain of a drying oil predominantly consisting of glycerides of linoleic and oleic acids, at

the reaction being wholly between the one o! the group and the oil and continuing the heating until a substantial quantity of the one of the group is combined at an intermediate point in the carbon chain of the fatty acid of the oil.

20. A condensation product of a drying oil pre-. dominantly consisting of glycerides of linoleic and oleic acids combined at a double bond with one of the group consisting of maleic acid and its anhydride, compounds which yield the same under the conditions of the reaction, alkyl-substituted maleic acids having less than ten carbon atoms in their carbon chains and maleic esters, by heating at a temperature in excess of 150C the reaction being wholly betweenthe one of the group and the oil, and continuing the heating until a substantial quantity of the one of the group is combined at an intermediate point in the carbon chainof the fatty acid of the oil and in the proportions of not substantially-more than enough of the one of the group to saturate the oil.

v21. A reaction product 01' maleic anhydride combined with linseed oil by heating at a temperature not less than 150 C. and in excess or the ordinary boiling point of the maleic anhydride with returncondensation and for a time sufllcient to produce a substantial amount 01' the' tions of not substantially more than enough of to saturate the oil. 

